CN102744064A - Catalyst for treating nitrogen oxide contained in tail gas of automobile and preparation method thereof - Google Patents

Catalyst for treating nitrogen oxide contained in tail gas of automobile and preparation method thereof Download PDF

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CN102744064A
CN102744064A CN2012102570693A CN201210257069A CN102744064A CN 102744064 A CN102744064 A CN 102744064A CN 2012102570693 A CN2012102570693 A CN 2012102570693A CN 201210257069 A CN201210257069 A CN 201210257069A CN 102744064 A CN102744064 A CN 102744064A
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catalyst
carrier
preparation
cerium
aluminium
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CN102744064B (en
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王秀云
王瑞虎
洪茂椿
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention provides a catalyst for treating nitrogen oxides contained in a tail gas of an automobile and a preparation method thereof. The catalyst takes aluminum-cerium-zirconium as a carrier and a small amount noble metals as active metals, the NOx conversion rate and the thermal stability of the catalyst are enhanced through the doping of rare-earth elements; after the catalyst is aged for 100 hours, the NOx purifying rate of the catalyst is basically kept unchanged, and the NOx purifying rate of an undoped catalyst is reduced by more than 20 percent.

Description

Be used for catalyst and preparation thereof that the vehicle exhaust nitrogen oxide is handled
Technical field
The invention belongs to the nano-catalytic application, be specifically related to a kind of rare earth doped aluminium-cerium-zirconium carrier and be applied to NO in the vehicle exhaust xPurification.
Background technology
In recent years, along with the rapid increase of automobile quantity, the tail gas of motor vehicle emission has become one of primary pollution source of atmosphere pollution, the NO in its composition xThe serious harm environment and the public's is healthy.China is at present to NO xPurify and generally adopt three-way catalyst, owing to receive engine air-fuel ratio to influence very big, traditional three-way catalyst NO xClean-up effect not good.So (Kong Ranbi > under the lean-burn condition; 1) NO xPurification is one of current challenging problem.The research of exhaust of lean-burn automotive purification at present mainly concentrates on NO xDirectly decompose, select catalytic reduction and NO xAspects such as storage-reduction, wherein NO xThe storage-reduction technology comes into one's own owing to plurality of advantages such as purification efficiency are high, temperature window is wide, operating cost is low day by day.
NO xThe basic principle of storage-reduction method is with NO under lean-burn condition xAbsorption stores, and under richness combustion condition, discharges then, changes into N through reducing agent 2Pt/Ba/Al wherein 2O 3Be typical NO xStorage-reduction catalyzer is at present in Japan's suitability for industrialized production.But the sulfur content in fuel on the Japanese market is low, and some domestic sulfur contents in fuel are higher, are that catalyst is poisoned easily, so Pt/Ba/Al 2O 3Catalyst is restricted in the practical application at home.In addition, NO xThe heat endurance of storage-reduction catalyzer also is pressing issues being badly in need of solution, at high temperature stores composition BaO and carrier A l 2O 3Or CeO 2In conjunction with generating BaAlO 4Or BaCeO 3Thereby inactivation.We find the difference through the rare earth element ion radius, get in aluminium-cerium-zirconium support crystal lattice, produce more oxygen vacancies, can effectively suppress BaAlO 4Or BaCeO 3Generation, thereby improve the heat endurance of catalyst.Also there are not pertinent literature and patent that this is reported at present.
Summary of the invention
It is high to the invention provides a kind of catalytic activity, the NO that stability is strong xCleaning catalyst.
This catalyst comprises aluminium-cerium-zirconium carrier and loads on one or more active components among precious metals pt, Pd and the Rh on this carrier, alkali metal or alkaline-earth metal storage component, and said aluminium-cerium-zirconium carrier is for modifying through rare earth element.
The said NO that is used for xThe catalyst that purifies, said carrier components comprises Al 2O 3, CeO 2And ZrO 2
The said NO that is used for xThe catalyst that purifies, the rare earth elements such as aluminium-cerium-zirconium carrier doping La, Y, Sm, Nd and Pr that this catalyst adopts.Rare earth element accounts for the 1-10 % (calculating with La or Nd) of aluminium-cerium-zirconium carrier quality.Preferred 5%.
The said NO that is used for xThe catalyst that purifies, the noble metal of dipping be among Pt, Pd and the Rh one or more.Preferred Pt.
Described NO xCleaning catalyst, reactive metal weight account for the 0.5-1 % of total catalyst weight.
Described NO xCleaning catalyst, one or more in the alkaline-earth metal such as this catalyst employing Li, Na, K, Rb alkali metal or Mg, Ca, Ba, Sr are auxiliary agent.Preferred Ba, K, wherein the mass fraction of Ba, K accounts for 16 % (calculating with Ba) of carrier.
Described Preparation of catalysts method comprises the synthetic of fresh appearance, again through 500 ° of C-700 ° of C roastings.
Its sintering temperature is preferably 550 ° of C.
Through La, Y, the doping of Nd or Pr has improved NO xThe heat endurance of cleaning catalyst, its active maintenance, stablize behind aging 100 h of 350 ° of C.
Description of drawings
Fig. 1 is: doped with rare-earth elements La, and Y, Nd and unadulterated Pt/Ba/ACZ catalyst n O change into NO 2Activity.
Fig. 2 is: doped with rare-earth elements La, Y, Nd and unadulterated Pt/Ba/ACZ catalyst n O xConversion rate curve.
Fig. 3 is: doped with rare-earth elements La, Y, Nd and unadulterated Pt/Ba/ACZ catalyst thermally-stabilised.
The specific embodiment
The present invention is used for NO xThe catalyst that purifies can use with particle form, also can be used as coating and is carried on the monolithic porous matrix and forms integral catalyzer.Monolithic porous matrix can be cellular cordierite, and ceramic matrixs such as mullite also can be other alloy substrates.
NO of the present invention xCleaning catalyst can be carried on separately on the matrix, also can mix with present three-way catalyst and form a multicomponent catalyst.
More specifically catalyst of the present invention is explained below in conjunction with embodiment, but these embodiment do not have any restriction to scope of the present invention.
Embodiment 1
(1) preparation of comparison sample: with Al (NO 3) 3 .6H 2O, Ce (NO 3) 3 .6H 2O and Zr (NO 3) 4 .5H 2O wiring solution-forming, wherein Al 2O 3: CeO 2: ZrO 2Mass percent be 67:22:11.Add 30 % H then 2O 2As oxidant, use NH 3 .H 2O is 10 as precipitating reagent to pH, and the centrifugal washing of process is with H 2PtCl 6 .6H 2O is distributed in the above-mentioned slurries, and is aging, and oven dry is behind 550 ° of C roasting 4 h, with Ba (NO 3) 2Adopt the incipient impregnation mode to be impregnated on the carrier of gained after the roasting oven dry.Through 500 ° of CH 2/ N 2Reduction back gained catalyst is Pt/Ba/ Al 2O 3-Ce 0.67Zr 0.33O 2Catalyst is designated as catalyst 1.
(2) preparation of doping lanthanum catalyst: with Al (NO 3) 3 .6H 2O, Ce (NO 3) 3 .6H 2O, Zr (NO 3) 4 .5H 2O and La (NO 3) 3 .6H 2O wiring solution-forming, wherein Al 2O 3: CeO 2: ZrO 2=67:22:11 adds 30 % H 2O 2, La 2O 3Be 5% of carrier quality, with 30 % H 2O 2As oxidant, NH 3 .H 2O is a precipitating reagent, and being precipitated to pH is 10, through centrifugal washing, with H 2PtCl 6 .6H 2O is distributed in the above-mentioned slurries, and is aging, and oven dry is behind 550 ° of C roasting 4 h, with Ba (NO 3) 2Adopt the incipient impregnation mode to be impregnated on the carrier of gained after the roasting oven dry.Through 500 ° of C H 2/ N 2Reduction back gained catalyst is Pt/Ba/La 2O 3-Al 2O 3-Ce 0.67Zr 0.33O 2Catalyst.Be designated as catalyst 2.
Embodiment 2
(1) preparation of comparison sample: with Al (NO 3) 3 .6H 2O, Ce (NO 3) 3 .6H 2O and Zr (NO 3) 4 .5H 2O wiring solution-forming, wherein Al 2O 3: CeO 2: ZrO 2Mass percent be 67:22:11.Add 30 % H then 2O 2As oxidant, use NH 3 .H 2O is 10 as precipitating reagent to pH, and the centrifugal washing of process is with H 2PtCl 6 .6H 2O is distributed in the above-mentioned slurries, and is aging, and oven dry is behind 550 ° of C roasting 4 h, with Ba (NO 3) 2Adopt the incipient impregnation mode to be impregnated on the carrier of gained after the roasting oven dry.Through 500 ° of CH 2/ N 2Reduction back gained catalyst is Pt/Ba/ Al 2O 3-Ce 0.67Zr 0.33O 2Catalyst is designated as catalyst 1.
(2) doping neodymium Preparation of catalysts: with Al (NO 3) 3 .6H 2O, Ce (NO 3) 3 .6H 2O, Zr (NO 3) 4 .5H 2O and Nd (NO 3) 3 .6H 2O wiring solution-forming, wherein Al 2O 3: CeO 2: ZrO 2Mass percent be 67:22:11, add 30 % H then 2O 2As oxidant, with NH 3 .H 2O is a precipitating reagent, and being precipitated to pH is 10, through centrifugal washing, with H 2PtCl 6 .6H 2O is distributed in the above-mentioned slurries, and is aging, and oven dry is behind 550 ° of C roasting 4 h, with Ba (NO 3) 2Adopt the incipient impregnation mode to be impregnated on the carrier of gained after the roasting.Oven dry.Through 500 ° of CH 2/ N 2Reduction back gained catalyst is Pt/Ba/Nd 2O 3-Al 2O 3-Ce 0.67Zr 0.33O 2Catalyst.Be designated as catalyst 3.
Below the performance of embodiment catalyst is estimated
Catalyst is to NO under test case 1 different temperatures xConversion ratio
Adopt each 0.5 mL of catalyst of embodiment 1-2 respectively, air speed 72 000 h -1, on the miniature fixed bed of continuous-flow, carry out NO xStore and determination by reduction NO in the tail gas xChange in concentration is through chemiluminescence NO-NO 2-NO xThe analyzer detection (Thermo, 42i-HL).Reacting gas consists of: 500 ppm NO, 8Vol%O 2, 8Vol%CO 2, N 2Be balance gas.Respectively at 200 ° of C, 250 ° of C, 300 ° of C, 350 ° of C, 400 ° of C measure catalyst down to NO xChanging effect, test result is seen Fig. 1, is example with 5 % rare earth elements (La or Nd) doped catalyst, test result of the present invention is not limited to the rare earth doped catalyst of 5 %.
As can beappreciated from fig. 1, described catalyst 2 and 3 has higher NO-to-NO than the catalyst 1 of doped with rare-earth elements not 2Conversion ratio.When 350 ° of C, catalyst 1,2 and 3 NO-to-NO 2Conversion ratio is respectively 33 %, 64 % and 43 %.
As can beappreciated from fig. 2, described catalyst 2 and 3 has NO preferably than the catalyst 1 of doped with rare-earth elements not xConversion ratio.T=350 ° of C, the NO of catalyst 2 xBe converted into N 2Conversion ratio be 98 %, the NO of catalyst 3 xConversion ratio is 94 %, and the NO of catalyst 1 xConversion ratio is 83 %.At 200 ° of C and 300 ° of its catalyst 2 of C NO than catalyst 1 xConversion ratio has improved more than 20 %.
The cycle life test of test case 2 catalyst 1-3
Reacting gas consists of: 500 ppm NO, 8 Vol%O 2, 8 Vol%CO 2, N 2Be balance gas.Air speed is 72 000 h -1, measuring NO behind aging 100 h on the continuous-flow fixed bed under 350 ° of C xThe stable ability of conversion ratio.Its result sees Fig. 3.
Fig. 3 catalyst 1 is at N 2After having stablized 100 h under the atmosphere, NO xConversion ratio reduces more than 20 %, deactivation phenomenom occurs.
Fig. 3 catalyst 2 is at N 2After having stablized 100 h under the atmosphere, NO xConversion ratio remains unchanged basically, deactivation phenomenom do not occur.
Fig. 3 catalyst 3 is at N 2After having stablized 100 h under the atmosphere, NO xConversion ratio also keeps not becoming basically.
The above is merely representative embodiment of the present invention, and is every according to modification and the change made in the claim of the present invention, all should belong to covering scope of the present invention.

Claims (10)

1. one kind is used for NO xThe catalyst that purifies; It is characterized in that: this catalyst comprises aluminium-cerium-zirconium carrier and loads on one or more active components among precious metals pt, Pd and the Rh on this carrier; Alkali metal or alkaline-earth metal storage component, said aluminium-cerium-zirconium carrier is for modifying through rare earth element.
2. catalyst according to claim 1 is characterized in that: said carrier components comprises Al 2O 3, CeO 2And ZrO 2
3. catalyst according to claim 1 is characterized in that: described rare earth element is selected from one or more among La, Y, Sm, Nd or the Pr.
4. according to claim 1 or 3 described catalyst, it is characterized in that: the doping of described rare earth element accounts for the 1-10 % of aluminium-cerium-zirconium carrier mass fraction.
5. catalyst according to claim 1 is characterized in that: described alkali metal is selected from one or more among Li, Na, K or the Rb; Described alkaline-earth metal is selected from one or more among Mg, Ca, Ba or the Sr.
6. like claim 1 or 5 described catalyst, it is characterized in that: described alkali metal or alkaline-earth metal account for the 10-16% of total catalyst weight.
7. catalyst according to claim 1 is characterized in that: described reactive metal weight accounts for the 0.5-1 % of total catalyst weight.
8. the described Preparation of catalysts method of claim 1 comprises the synthetic of fresh appearance, passes through 500-700 ° of C roasting again.
9. Preparation of catalysts method according to claim 8 is characterized in that: said sintering temperature is 550 °C.
10. the NO of the described catalyst applications of claim 1 in vehicle exhaust xPurification.
CN201210257069.3A 2012-07-23 2012-07-23 Catalyst and its preparation for nitrogen oxide in automobile exhaust processing Active CN102744064B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103551165A (en) * 2013-11-04 2014-02-05 中国科学院福建物质结构研究所 Transitional-element-doped nitrogen oxide purification catalyst as well as preparation method and application thereof
CN105709811A (en) * 2016-04-12 2016-06-29 青岛农业大学 Silver-doped calcium-magnesium composite storage-reduction catalyst for exhaust gas of engine as well as preparation method and application of catalyst
CN108686640A (en) * 2017-03-31 2018-10-23 丰田自动车株式会社 Exhaust gas purifying catalyst
CN109499622A (en) * 2013-05-17 2019-03-22 庄信万丰股份有限公司 Oxidation catalyst for compression-ignition engine
CN114588901A (en) * 2022-03-30 2022-06-07 北京工业大学 NO oxidation catalyst for removing NOx from ship and preparation method thereof

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CN101428219A (en) * 2008-11-14 2009-05-13 中国科学院上海硅酸盐研究所 Oxynitride catalysis reductant in oxygen-enriched condition and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109499622A (en) * 2013-05-17 2019-03-22 庄信万丰股份有限公司 Oxidation catalyst for compression-ignition engine
CN103551165A (en) * 2013-11-04 2014-02-05 中国科学院福建物质结构研究所 Transitional-element-doped nitrogen oxide purification catalyst as well as preparation method and application thereof
CN105709811A (en) * 2016-04-12 2016-06-29 青岛农业大学 Silver-doped calcium-magnesium composite storage-reduction catalyst for exhaust gas of engine as well as preparation method and application of catalyst
CN105709811B (en) * 2016-04-12 2017-11-07 青岛农业大学 A kind of Ag doping calcium and magnesium being used in motor exhaust is combined storage and reduction catalyst and its preparation method and application
CN108686640A (en) * 2017-03-31 2018-10-23 丰田自动车株式会社 Exhaust gas purifying catalyst
CN114588901A (en) * 2022-03-30 2022-06-07 北京工业大学 NO oxidation catalyst for removing NOx from ship and preparation method thereof

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